Typically low refractive index thin films are made utilising sol-gel processes or vacuum evaporation deposition techniques. The following prior art documents are but a few examples of methods used to produce low refractive index films made from silica.
WO 02/41043 is directed to a method of forming a meso-structured inorganic/block copolymer composite or inorganic porous solid doped with a dye or dye sensitive agents, formed by creating a silica sol-gel from tetraethoxysilane (TEOS), ethanol and water. The sol-gel is then templated with block copolymers, such as poly(ethylene oxide)-poly(alkyene oxide)-poly(ethylene oxide). The inorganic/organic composite is then calcined or subjected to solvent extraction to remove excess block copolymer species, prior to doping with dye/dye sensitive agents.
U.S. Pat. No. 6,379,776 is directed to a multi-layer, anti-fogging and stain preventing glass coating comprising an alkaline shut-off film, a silica oxide/zirconium oxide composite, and a photocatalytic film, of titanium oxide. Both the silica oxide/zirconium oxide composite layer and the titanium oxide layers are formed using known sol-gel processes.
US 2002/0090519 describes a method of hydrolytically polycondensing tetraalkoxysilanes to form a silica oxide sol. The hydrolytic polycondensation occurs by placing the tetraalkoxysilane in an aqueous alcohol ammoniacal solution to encourage hydrolysis of the tetraalkoxysilane and produce silica oxide particles. The sol is subject to steam distillation in order to remove the alcohol and ammonia prior to the pH being adjusted to between 3 and 8. Surfactants are then added to the silica sol to act as pore templates during the coating of a substrate. The coating is calcined to cure the silica film and remove the surfactants.
U.S. Pat. No. 5,948,482 is directed to a method of forming an aerogel thin film at ambient pressure, by forming a silica oxide sol-gel using standard processes before derivatizing the surface of the gel with a hydrolysable organic substituent, reliquefying the sol with sonication and depositing the gel onto a substrate.
U.S. Pat. No. 5,698,266 is directed to a modification of the standard sol-gel method of forming an anti-reflective coating by mixing ethanol, tetraethoxysilane (TEOS) and ammonia and hydrolysing for up to 48 hours to form a colloidal silicon oxide suspension dispersed in an aliphatic alcohol. The silica sol is then filtered to obtain silica particles for deposition onto a substrate, prior to drying. The coated substrate is placed in an ammoniacal environment for up to twelve hours to form an anti-reflective coating. This final step is claimed to improve the binding between the silica particles, and so renders the film more robust.
C. Shelle et al, J. Non-Cryst. Solids, 218, pg 163, 1997, describes a method of producing anti-glare glass films using sol-gel coatings formed from methyltriethoxysilane, tetraethoxysilane and tin oxide. The sol-gel is aged at 0° C. prior to deposition onto a substrate and calcining at 500° C.
G Wu, et al, J. Non-Cryst. Solids, 275, pg 169, 2000, describes a method of creating a sol-gel, in which tetraethoxysilane (TEOS) is catalysed in a two step acid-base process. The TEOS is initially aged in an ammonia-ethanol solution, pH adjusted, refluxed and a second pH adjustment made. In preparing the films, G. Wu et al deposit the sol-gel onto a substrate and expose to an ammoniacal environment.
Hass D. D. et al, NASA Contractor Report, 201733, teaches the coating of fibrous insulation with a reflective film such as silica, titanium dioxide, zirconium oxide and/or combinations thereof. The oxides are formed using known sol-gel processes into which the fibrous insulation is submersed to coat the fibres prior to vacuum or heat drying.
The above processes which rely on sol-gel techniques for producing thin films are complex, multi-step processes which are costly, involve high temperature steps in fabrication, and/or require a surfactant for templating. The films produced by these sol-gel processes are typically easy to damage and/or liable to delamination.
One of the few prior art processes for producing silica coatings without directly following the conventional sol-gel process is described in U.S. Pat. No. 6,231,989 assigned to Dow Corning Corporation. The patent describes a process of forming a coating from a solution comprising a resin containing at least two Si—H groups in a solvent, such as methylisobutylketone. The solution is coated to a substrate with about 5% of the solvent remaining in the coating. An aqueous basic catalyst causes condensation of the Si—H groups. The solvent is evaporated to leave a porous coating. In summary, the method uses an ammonia vapour step to improve adhesion and mechanical strength of the resultant film, but relies in the main part upon conventional sol-gel methods to produce the coating at room temperature and pressure. The preparation of suitable starting materials containing two Si—H groups is difficult, which limits the usefulness of the technique.